The development of photoelectrodes capable of light-driven hydrogen evolution from water is an important approach for the storage of solar energy in the form of a chemical energy carrier. However, molecular catalyst-based photocathodes remain scarcely reported and typically suffer from low efficiencies and/or stabilities due to inadequate strategies for interfacing the molecular component with the light-harvesting material. In this study, we report the straightforward preparation of a p-silicon|mesoporous titania|molecular catalyst photocathode assembly that is active towards proton reduction in aqueous media with an onset potential of +0.4 V $vs.$ RHE. The mesoporous TiO$2$ scaffold acts as an electron shuttle between the silicon and the catalyst, while also stabilising the silicon from passivation and enabling a high loading of molecular catalysts (>30 nmol (geometrical cm)$\mathrm{<mrow\; data-mjx-texclass="ORD">-2</mrow>}$). When a Ni bis(diphosphine)-based catalyst is anchored on the surface of the electrode, a high turnover number of ~1 x 10$3$ was obtained from photoelectrolysis under UV-filtered simulated solar irradiation at 1 Sun after 24 h at pH 4.5. Notwithstanding its aptitude for molecular catalyst immobilisation, the p-Si|TiO$2$ photoelectrode showed great versatility towards different catalysts and pH conditions, with photoelectrocatalytic H$2$ generation also being achieved with platinum and a hydrogenase as catalyst, highlighting the flexible platform it represents for many potential reductive catalysis transformations.